Certain polyepoxide treated amine modified thermoplastic phenol-aldehyde resins and method of making same



Melvin De Groote, St. Louis, and Kwan-Ting Shen, Brenta mt wood, M0., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Original application February. 24, 1953, Serial No. 338,575, now Patent No. 2,771,437, dated November 20, 1956. Divided and this application May 1, 1956, Serial No. 582,043

14 Claims. (Cl. 260-45) The present invention is a continuation-in-part of our co-pending application, Serial No. 305,079, filed August I or compounds useful'as demulsifying agents in processes or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

method of first condensing certain phenol-aldehyde resins, hereinafter described in detail, with certain basic nonhydroxylated polyamines, hereinafter described in detail, and formaldehyde, which condensation is followed by reaction of the resin condensate with certain phenolic p'olyepoxides, also hereinafter described in detail, and cogenerically associated compounds formed in the preparation of the polyepoxides.

In preparing diepoxides or the low molal polymers one does usually obtain cogeneric materials which may include monoepoxides. However, the cogeneric mixture is invariably characterized by the fact that there is on the average, based on the molecular weight, of course, more than one epoxide group per molecule.

A more limited aspect of the invention is represented by the reaction product of (A) an amine-modified phenolaldehyde resin condensate as described, and (B) a member of the class of (1) compounds of the following formula:

and (2) cogenerically associated compounds formed in the preparation of (1) preceding.

It so happens that the bulk of information concerned with the preparation of compounds having two'oxirane rings appears in the patent literature and for'the most part in the recent patent literature. Thus, in the subsequent text, there are numerous references to such patents The products of our invention are obtained by the kept in mind. The epoxides, and particularly thediepoxides may have no connecting bridge between the phenolic nuclei as in the case of a diphenyl derivative or may have a variety of connecting bridges, i. e., divalent linking radicals. Our preference is that either diphenyl compounds be employed or else compounds where the divalent link is obtained by the removal of a carbonyl oxygen atom, as derived from a ketone or aldehyde.

If it were not for the expense involved in preparing and purifying the monomer we would prefer it to any other form, i. e., in preference to the polymer or mixture of polymer and monomer.

Stated another way we would prefer to use materials of the kind described, for example in U. S. Patent 2,530,353, dated November 14, 1950. Said patent describes compounds having the general formula mo on-on,-o R.

wherein'R is an aliphatic hydrocarbon bridge, each n independently has one of the values 0 and 1, and X is an alkyl radical containing from 1 to 4 carbon atoms.

The list of patents hereinafter referred to in the text as far as polyepoxide goes, is as follows:

U. S. Patent No. Dated inventor 2,122,958 July 5, 1938 Sehafer. 2,139,766...- December 13, 1938 Mikeska et 81. 2,174,248... September 26, 1939- Do. 2,195,539. April 2, 1940. Do.

207,719 July 16, 1940. Cohen et 8.1 2,244,021. June 3, 1941. Rosen et 9.1 2,246,321 June 17, 1941 Rosen, 2,285,563 June 9, 1942. Britten e't al. 2,331,448 October 12, 1943 Wlnnlng'et a1. 2,430,002 November 4, 1947 De Groote et al. I 2 457.329 Swern et a1. 2,462,047 Wyler. 2,462,048 Do. 2,482,748 Dletzler.

488,134. Mikeska et a1, 2,503,196 Dletzler et a1; 2,504,064 Beck et 8.1. 2,506,486 Bender et al. 2,515,906 Stevens et a1.

2 515,907 Do. 2,515,908 D0. 2,526.545 Dletzler. 2,530,353 Havens. 2,564,191.... August 14, 1951.. De Groote et al. 2,575,558 November 20, 1951---. Newey et 21. 2,581,464 January 8, 1952... eeh. 2,581,919. -...do. .Albert. 2,582,985.... January 22, 1952... Greenlee.

The compounds having two oxirane rings and employed for combination with the reactive amine-modified phenolaldehyde resin condensates as herein described are compounds of the following formula and cogenerically associated compounds formed in their preparation:

H, HY", .a

the 1 divalent ll C radical, the divalent sulfone radical, and the divalent monosulfide radical S-, the divalent radical V and the divalent disulfide radical -SS;-and R 0 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom'and a nuclear hydrogen atom from the phenol V in whichRZR", and R represent a member of the class of hydrogenand hydrocarbon substi-tuents of thearomatic nucleus, said substituent member having not over 18 carbon atoms; n represents an integer selected from the class of zero and '1, and n represents a-,whole number not greaterthan 3. Theabove mentioned compounds and those cogenerically associated compounds formed in their preparation are thermoplastic and organic solventsoluble. Reference to being thermoplastic characterizes them as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus dilferentiates them from infusible resins. Referenceto being soluble in an organic Solvent means any of the usual organic solvents, such as alcohols,

are

compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from ahydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins. Note, for example, that said U. S. Patent No. 2,494,295 describes products wherein the epoxide derivative can combine with a sulfonamide resin. The invention in said U. S. Patent 2,494,295, of course, is to obtain ultimately a suitable resinous product having the characteristics of acomparatively insoluble resin.

Having obtained areactant having generally 2 epoxy rings as depicted'in the last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any amine-modified phenol-aldehyde resin by virtue of the fact that there are always present reactive hydroxyl groups which are part of the phenolic nuclei and there may be presentreactive hydrogen atoms attached to a nitrogen atom, orv an oxygen atom, depending on'the presence of :a hydroxylated group or secondary amino group.

To illustratetheproducts which represent the subject matter of the present invention reference will be made to a reaction involving a .mole of the oxyalkylating agent, i. e., the compound having two oxirane rings and an amine condensate. Proceeding with the example previously described'it is obvious the reaction ratio of two moles of the amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

(condensate) ketones, esters, ethers, mixed solvents, etc. Reference to solubility-is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings before reacting with the amine-modified resin. In such instances, of course, the solvent selected would have. to beone which is not susceptible to oxyalkylation, as forcxample, kerosene, benzene, toluene, dioxane, variousketones,chlorinated solvents, dibutyl ether,rdihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol. '1 V The expression epoxy-- isnot usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring i-s'sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word fepoxy unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a-co'mpound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least4 carbonatomsand is V formally'described as 1,2-epoxy:3,4-epoxybutane (1,2-3,4

diepoxybutane) It well may be that even though the previously sug- (condensate) in which thevarious characters have their previous significance and the characterization condensate is simply an abbreviation for the condensate which is described in greater detail subsequently.

Such final product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, orifor that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid,

"preferred compounds have distinct water solubility or are distinctly dispersible in 5% gluconic acid. For instance, the products freed from any solvent can be shaken with Q 5 to 20 times their weight of 5% distilled water at ordinary temperature and. show at least some tendency towards beingself-dispersing. The solvent which is generally tried is xylene. "If xylene alone does not serve then a mixture gested-formula represents-the principal component, or

components, of the resultant or reaction product described in the previous text, it maybe important to, note that somewhat similar compounds, generally of much-higher 7 molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydrie phenols containing an average of more than one epoxide group per'molecule and free from functional groups other than epoxide and hydroxyl groups. See U. S. Patent No. 2,494,295, dated January 10,1950, to Greenlee. The

of xylene and methanol, for instance, 80 parts of xylene and 20 parts of methanol, or parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a srnall-amountpfacetone to the xylene-methanol mixture,:for'instance, 5% .to 10% of acetone.

7 action with ethylene 'The ,polyepoxide-treated condensatesobtained in the m annerdescribed are, in turn, 'oxyalkylation-susceptible and valuable-derivatives :can be obtained by further re oxide, propylene oxide, ethylene imine,:etc. I

:.Similarly,-.:the'..polyepoxide ,derived compounds can be reacted-with a product, having both anitrogen'group and a l,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for example for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the Water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sufficiently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al.

In said patent such test for emulsification using a waterinsoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the. obvious chemical equivalent or equivalent chemical test can'be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience what is said hereinafter will be divided into nine parts with Part 3, in turn, being divided into three subdivisions:

Part 1 is concerned with our preference in regard to the polyepoxide and particularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

Part 3, Subdivision A, is concerned with the preparation of monomeric diepoxides, including Table I;

Part 3, Subdivision B, is concerned with the preparation of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin.

Part 5 is concerned with basic nonhydroxylated polyamines having at least one secondary amino group and having not over 32carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine befree from any primary amino "6 radical, any substituted imidazoline radical and any substituted tetrah'ydropyrimidine radical; and

Part 6 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to reaction with polyepoxides;

Part 7 is concerned with the reactions involving the two preceding types of materials and examples obtained by such reaction. Generally speaking, this involves nothing more than a reaction between 2 moles of a previously prepared amine-modified phenol-aldehyde resin condensate as described, and one mole of a polyepoxide so as to yield a new and larger resin molecule, or comparable product;

Part 8 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products; and

Part 9 is concerned with uses for the products herein described, either as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 As willbe pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solventsoluble liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. It is generally obtained from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of the epoxides usually results in the formationv of a co-generic mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually expensive. If monomers were available commercially at a low cost, or if they could beprepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been prepared and described in the literature and will be referred to subsequently. However, from a practical standpoint one must Weigh the advantage, if any, thatthefimonomer has over other lowmolal' polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molal polymers in comparatively small amounts. Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present. free from monomers and still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances where the phenolic nuclei are either united direct ly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrateone class. The diphenyl derivatives illustrate a Indeed, the mixture can be prepared 7 second class,;.ai1d-lthe materials obtained by reacting. sub stituted monofunctional phenols with an'aldehyde. illus-.

traterthe'third class. All :the various known classes may be-used but; our preference rests with these classes due.

totheir availability and ease of preparation, and also due to the fact that the cost is lower than in other. examples.

Although the .diepoxide reactants can be produced in more thanwone way, as pointed out'elsewhere, ourpreference .is to; produce them bymeans of the. epichlorohydrin reaction referred to in detail subsequently.)

One epoxide' which can be purchased in the open market and contains only a modest amount-of polymers corresponds to the derivativeof bis-phenol A.. It'can be used as such, or the monomer can be separated-by any Reference hasjust been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with the 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2"'iso rners being present. It' is immaterial which one of these isomers isused and the commercially available mixture isentirely satisfactory.

Attention is again directed to the fact that in the instant part, to wit, Part 1, and in succeeding parts, the text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution of one compound for the other wouldbe required. Thus, what is said hereinafter, although directed to-0ne class or a few classes, applies withequal force and efiectxto the other classes of epoxide reactants.

If sulfur-containing compounds are prepared they should be freed fromimpurities with considerable care for the reasonthat any time that a lo-w-rnolal sulfur-containing compound. can react with epichlorohydrin there may be ,formed a ,by-product in. which the chlorine happened to be particularly reactive and -may represent a product, or,a mixture of products, which would be unusually toxic, even though in comparatively small concentration,

PART 2 The polyepoxides and particularly the diepoxides can be derived by more than one method as, for example, the use of epichlorohydrin or glycerol dichlorohydrin. If a product such as bis-phenol A is employed the ultimate compound in monomeric form employed as a reactant in the. present invention has the following structure:

CH3 H H H H H H 0 CH3 0 Treatment with epichlorohydrin, for example, does. not yieldthis product initially but there is an intermediate produced which can be indicated bythe following structure:

CH: H -H' H H H H 36 7 7 3. 1 A H' 7 'I H I C 7 0 335., OHWCAA It would be immaterial Actually, what may happen for any one of a number of reasons is thatoneobtains a product in which there is only one epoxide ringand there may, as a matter of fact/be morethan onelhydroxy radical as illustrated by the following compounds CH3 H: Hv lH l' Y H :n H newo gfo 13 og l3oH I 0 any OH or or V V V om H- H H l H H H- T/ 1? EG t i '0' our 011' be (2 Even one starts with the reactants in the preferred ratio, to wit, two parts of epichlorohydrin to one part of bis-phenol A, they. do net necessarily so react and as a result one may obtain products in which more than two epichlorohydrinresidues.become attached to a single bis-phenol A nucleus by virtue oft'ne reactive hydroxyls present which enter into oxyalkylation reactions rather than ring closure reactions.

(3) As is well known, ethylene oxide in the presence of alkali, and for that matter in the complete absence of water, forms cyclic polymers Indeed, ethylene oxide can produce a solid polymer, This same reaction can, and at times apparentlydoes, take place in connection with compounds having one, or in the present instance, two substitutedoxirane rings, i. e., substituted 1,2 epoxy rings. Thus, in many ways it is easier to produce a polymer, particularly a mixture of the monomer, dimer and trimer, than itis to producethe monomer alone.

(4) As has been pointed out previously, monoepoxides may be present-and, indeed, are almost invariably and inevitably present when one attempts to produce polyepoxides, and particularly diepoxides. The reason is the one which has bcen indicated previously, together with may reactwith a moleof bis-phenol A to give a monoepoxy structure. Indeed, in the subsequent text immediately following .reference'is made to the dimers, trimers and tetramers in which two epoxide groups are present. Needless torsay, compounds can be formed which correspond inevcry respect except that one terminal epoxide group is absent and in its place is a group having one chlorineatom and one hydroxyl group, or else .two hydroxyl groups, or an unreacted phenolic ring.

(5) Somereferencehas been made to the presence of a chlorine atom and although all eflort is directed towards the elimination of any chlorine-containing molecule yetit'is apparent that this is often an ideal approach rather thana practical possibility. Indeed, the same sort of reactants are sometimes employed to obtain products in which intentionally there is both an epoxide group and a chlorine atompresent. See U. S. Patent No. 2,581,464, dated January8,- 1952, to Zech.

Whathas been said in regard to the theoretical aspect 'is,; ,of: :.Ql IS@l-. .Qlp6ly.,-,related to the actual. method of 9 16 preparation which is discussed in greater detail in Part 3, an average of more than one epoxide group per molecule particularly Subdivisions A and B. There can 'be no and free from functional groups other than epoxide and clear line between the theoreticalaspect and actual prehydroxyl groups. parative steps.. However, inorder to summarize or illus- Referring now to what has been said previously, to

trate what has been said in Part 1, immediately preceding wit, compounds having both an epoxy ring or the equiva reference will be made to a typical example which allent and also a hydroxyl group, 0ne need go no further ready has been employed for purpose of illustration. than to consider the reaction product of The particular example is e e CH It is obvious that two moles of such material combine readilyrwith one mole of bis pheno1 A, reactant would yield a product having an unreacted epoxy ring and two reactive hydroxyl radicals. Referring again to a previous formula, consider an example where two O O moles of bisphenol A have been reacted with 3 moles of 41H; epichlorohydrin. The simplest compound formed would to produce the product which is one step further along, 1 belthusil and bisphenol A in a mole-for-mole ratio, since the initial o .e e V 0 H3 CH- at least, towards polymerization. In other words, one Such a compound is comparable to other compounds prior example shows the reaction product obtained from having both the hydroxyl and epoxy ring such as 9,10-

one mole of the bisphenol A and two moles of epichloroepoxy octadecanol. The ease with which this type of hydrin. This product in turn would represent three moles compound polymerizes is pointed out by U. S. Patent of bisphenol A and four moles of epichlorohydrin. No. 2,457,329, dated December 28, 1948, to Swern et al.

For purpose of brevity, without going any further, the The same difiiculty which involves the tendencyto polynext formula is in essence one which, perhaps in an merize on the part of compounds having a reactive ring idealized way, establishes the composition of resinous and ahydroxyl radical may be illustrated by compounds products available under the name of Epon Resins as where, instead of the oxirane ring (1,2-epoxy ring) there now sold in the open market. See, also, chemical pamis present a 1,3-epoxy ring. Such compounds are derivaphlet entitled Epon Surface-Coating Resins, Shell Chemtives of trimethylene oxide rather than ethylene oxide. ical Corporation, New York city. The word Eponf is 7 f1 See U. S. Patents Nos. 2,462,047 and 2,462,048, both a registered trademark of the Shell Chemical Corporation. dated February :15, 1949, to Wyler.

z but cm on,

- For the purpose of the instant invention,-n' mayrep- At theexpense O rep ti ion 10f What appeared pree t a number i l di o, d at h most a 1 viously, it may be well to recall that these materials may number such as 1, 2 or 3. This limitation does not exist vary from simple Soluble non-resinous to Complex soluble resinous epoxides whichare polyether derivatives of polyhydric phenols containing an average of more than one epoxide group per molecule and free from functional' groups other than epoxide and hydroxyl groups.

g fi g g i5 gga i ig gzg fig gg g if f 2 The former are here included, but the latter, i. e., highly y y resinous or insoluble types, are not,

best, an over-simplification, or at the most represents 60 In Summary then in light of what has been Said in actual eiforts to obtain resins as differentiated from the herein described soluble materials. It is quite probable that in the resinous products as marketed for coating use p p y the more important orprincipa'l constituent ounds suitable for reaction with amines may be sumor constituents. These materials may vary from simple marized by the following formula:

H; H H: @I Ha I H: 1 H! H H! non-resinous to complex resinous epoxides which are or for greater simplicity the formula could be restated polyether derivatives of polyhydric phenols containing; thus:

in which the various characters have their prior sig-'- diphenols, which'are sometimes referred to asdiglycidyl nificance and in which R 0 is the divalent radical obethers, have been described in a number of patents, For tained by the elimination of a hydroxyl hydrogen atom v i n r f c will be mad to two only,to wit, and a nuclear hydrogen atom from the Phenol aforementioned ,U. S. Patent 2,506,486, and aforementioned U. S. Patent No. 2,530,353.

Purely by way of illustration, the following diepoxides,

I 1 or diglycidyl ethers as they are sometimes termed,'are included for purpose of illustration. These particular compounds are described in the two patents 'just in which R, R", and R' represent a member of the class mentioned.

TABLE I Ex- Patent ample Dtphenol I Dlglycldyl ether refernumber V ence CH (C H OH Di(epoxypropoxyphenyl)methane....- 2,506,486 CllgCl n HgHh Di(epo rypropoxyphenyhrnethylmethane. 2, 506,486 (CH3)2C(C5H4OH)2 Di(epoxypr0poxyphenyl)dimethylmethane 2,506,486 C H C(CH3)(CsH4OH)z.. Di(epoxypropoxyphenyl)ethylmethylmethane- 2,506,486 (OzHshC (CsHiO H); Di(epoxypropoxyphenyl)diethylmethane e 2, 506, 486 CH3C(C3H )(C BH OH) Di(epoxypropoxyphenyl)methylpropylmethane 2, 506, 486 GHBC (Cal-I5) (Cal-140E) z... Di(epoxypropoxyphenyl)methylphenylmethane 2, 506, 486 CgH5C(CsH5)(CsH4OI-I)z D1(epoxypropoxyphenyl)ethylphenylmethane. 2, 506, 486 CsH1C C511 (06114011) 2" Dr(epoxypropoxypheny1) propylphenylmethane 2, 506, 486 C4H9C (0 1 1 (CBHiOH) D1(ep0xyprop0xypheny1) butylphenylmethane 2, 506, 486 (CHsCuH4)CH(C6H4OH)i Di(epoxypropoxyphenyl)tolylmethane. 2, 506, 486 (CHzCeHs) C (CH1) (0 1340 Di(ep0xypr0poxyphenyl) tolylmethylme 2, 506, 486 Dihydroxy diphenyl 4,4-bis(2,3-ep0xypr0p0xy)d1phen 2, 530, 353 (CH3) C(C4H5.C5H3OH)2 2,2-bis(4-(2,3-epoxypropoxy)2-tertiarybutyl phenyl)pr0pane 2, 530,353

consisting of hydrogen and hydrocarbon substituentsof Subdr'yiszbn B the aromatic nucleus, said substituent member havlng not 30 A816 the preparation of lowmwlal polymeric eppxides aver 1&81 calrbon fatoms; ndrelpreseints an integer selelclteld or mixtures reference is made to numerous patents and mm 6 c ass 0 Zero an an n repress S a w o e particularly the aforementioned U. S. Patents Nos. number not greater than 3. 2-575 558 and 2 582 985 PART 3 V In ;light of the aforementioned U. S. Patent No. 352,575,558, the following examples can be specified by Subdzvzszon A The preparations of the diepoxy derivatives of the in mind it is in'essence an over-simplification.

' TABLE 11 I C--C-C- +OR1[R],.R1O-.CC-C- ,OR .[R].,-R OCC-C H2 H -H2 r (1)11 H: H H:

(in which the characters have their previous significance) Example R1O from HR1OH I R n n 7 Remarks,

number 7 Bl Hydroxy benzene... CH3 1 0,1,2 Phenol known as bis-phenol A. Low I polymeric mixture about or more -C- where n=0, remainder largely where I n=1, some where n'=2. CH3

B2 do CH 1 0,1,2 Phanolknownasbis-phenol B. Seenote V regarding Bl aboye I v r 7 CH2 7 V Bs 'Orthohutylphenol on; 1" 0,1,2 'E veri though was preferably 0, yet the l usual reaction productmight wellcon- -C- tairi materials'wh'ere 71/ is 1, or to a lesser degree 2. V QH; j "Bra.--" Orthoamylphenol c on, r .4 1 0,1,2 15

V T V V CHa B5 Orthooety v 115 V 1 (lx V V B6 OrthononylphenoLn, CllH 1 0,1,2 Do.

. (lgf B7 Orthododecylphenol 5. (EH; 1 0,1,2 Do.

c. 't JH:

reference to the formula therein provided one still bears The prior examples have been limited largely to those in which there is. no divalent linking radical, as in the case Subdivision C of diphenyl compounds, or where the linking radical is derived from a ketone or aldehyde, particularly a ketone. Needless to say, the same procedure is employed'in .converting diphenyl into a diglycidyl ether regardless of the Example n i 1: Remarks number B Metacres OH; 1 0,1,2 See prior note. This phenol used as 4 a I initial material is known as bis-phenol C- C. For other suitable bis-phenols see I U. 8. Patent 2,564,191. CH1

Be (3H1 1 0,1,2 See prior note.

310...--. Dlbutyl (ortho-para) phenol. 1g 1 0,1,2 Do.

. 11 1111...-.. Diamyl (ortho-para) phenolg 1 0,1,2 Do: l

m2 Dtoctyl (orthQ-para) phenol- 1g 1 0,1,2 D01 Dlnonyl(ortho-para)phenol. g 1 0,1,2 -Do1 v H 1514...-.. Dlamyl (ortho-para) phenol- 1g 1 0,1,2 D01 an: fln g 1 0,1,2 D01 I (EIHL 1316 Hydroxy benzene... 1 0,1,2 Do.

1111...-.. DiamylphenoHortho-para)- -s-s- 1 0,1,2 Do.

me an 7 s 1 0, 1, 2 Do. 1119....-. Dibutyl phenol (ortho-para)- g g 1 0,1,2 Do. H H 320 an V H H 1' 0,1,2 Do.

1-0-0- 11 E 1321....-. Dlnonylphenol(ortho-para)- I 1 15 1 0,1,2 7 no.

i H- H 322....-- Hydroxy benzene I? 1 0, 1, 2 Do.

B23 in N 0 0, 1,2 Do. B24 Ortho-lsopropyl phenol CH1 1 0,1,2 See prlornote. (As to preparation 014,4- lsopropylidene bis-(2isopropylphenol) see U. 8. Patent No. 2,482,748, dated ([3 Sept. 27, 1949, to Dietzler.) I B25 Para-octyl phenolg... CH;SCH=' 1 0,1,2 See prior note. (As to preparation of the v g phenol sulfide see U. 8. Patent No..

2,488,134, dated Nov. 15,.1949, to Mikeska et a1.)

B26 Hydro benzene CH1 1 0 1 2 See priornote. (As to reparation orthe xy phenol sulfide see 8. Patent No.

purpose of illustration attention is directed to numerous other diphenols which can berea'dily converted to a suitable polyepoxide, and particularly, diepoxide, reactant.

as in the instance of cyclohexylphenol or phenylphenol. nature of the bond between the two phenolic nuclei. For Such substituents are usually in the ortho position and may be illustrated by a phenol of the following composition:

Ho onr l Similar phenols which are monofunctional, for instance,

paraphenyl phenol or paracyclohexyl phenol with an additional substituent in the ortho position, may be employed in reactions previously referred to, for instance, 7

with formaldehyde or sulfur chlorides to give comparable phenolic compounds having 2 hydroxyls and suitable for subsequent reaction with epichlorohydrin, etc.

ing of secondary butyl and tertiary butyl groups and R is 31- O-El atoms, inclusive, and aryl and chloraryl radicals of the a substituent selected from the class consisting of alkyl,

cycloalkyl, aryl, aralkyl, and alkaryl groups, and wherein said alkyl group contains at least 3 carbon atoms. See U. S. Patent No. 2,515,907.

CsHn CsHu in which the --C H groups are secondary amyl groups. See U. S. Patent No. 2,504,064.

See U. S. Patent No. 2, 2,53}

on; n 2 13," a

See U. S. Patent No. 2,503,196.

ncl! wherein R is amember. of the gnoupconsisting of alkyl, and alkoxyalkyl radicals containing from 1 to 5 carbon V benzene series. See U. S. Patent No, 2,526,545. 0'

OH R:

wherein R is a substituent selected from the class con-' sisting of secondary butyl and tertiary butyl groups and R is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, :aralkyl, and alkaryl groups. See U. S. Patent :No. 2,515,906.

See U. s. Patent No. 2,515,908.

As to sulfides,v the following compound is of interest:

See U. s. Patent No. 2,331,44

I NOS- As to descriptions of various suitabl'e'phe'nol sulfides, reference is made to the following patents: U. S. Patents 2.246.321, .71 2 174 248 2.1 9.766 2,244,021, and 2,195,539.

As to sulfones, see U. S. Patent No. 2,122,958.

As to suitable compounds obtained by the use of pounds such as formaldehyde or some other aldehyde, particularly com- Alkyl yl in which R is a methylene radical, or 'a substituted methylene radical which represents the residue of an aldehyde and is preferably the unsubstituted. methylene radical derived from formaldehyde. See U. S. Patent No;

See also U. S. Patent No. 2,581,919 which describes di(dialkyl cresol) sulfides which include the monosulfides,

the disulfides, and the polysulfides. The following formula represents the various dicresol sulfides of this invention:

OH OH CH CH3 B2 ,R1"Rr B2 in which R and R 'are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R and R each preferably contain 3 to about 10 carbon atoms, and x is 1 to 4. The term sulfides as. used in this text, there;

fore, includes monosulfide, disulfide, and polysulfides.

17 'PART 4 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula OH OH OH H r H C C H I H i R R n R i In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 15 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessan'ly soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser. I

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or Xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,449,368, dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenatedorganic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. These resins are difunctional only in regard to methylol-forming reactivity, are derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following every case is to have the resin neutral."

Y f8 the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

R\ H oH oH OH H /R N-0 o- 0-- C-N H H H H \R,

R R n R The basic nonhydroxylated amine may be designed thus:

In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2

moles of amine may combine with one mole of the alde-j hyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if atj all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

made using an acid catalyst or basiccatalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. Inother words, if prepared by using a strong acid as a catalyst,

such strong acid should be neutralized. Similarly,'if a:

strong base is used as a .catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as; much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used.

However, the most desirable procedure in practically '19 In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily availablecommercially. For'purposes of convenience suitable resins are characterized in the following table:

TABLE III Mo]. wt

7 Ex- Position R of resin ample R of R derived n molecule number om- (based on n+2) Phenyl Para. 3. 5 992. 5

Tertiary butyl do 3.5 882.5 Secondary butyL Ortho-.. 3. 5 882. 5 CyclohexyL- 3. 5 1,025. 5 Tertiary amyl 3. 5 959. 5 Mixed secondary 3. 5 805. 5

and tertiary amyl. Propyl 3. 6 805. 5 Tertiary hexy 3. 5 1,036. 5 ct l 3. 5 1, 190. 6 Nonyl 3. 5 1, 267. 5 Decyl- 3. 5 1, 344. 5 Dodecyl 3. 5 1,498. 5 Tertiary butyl 3. 5 945. 5

Tertiary amyl 3. 5 1, 022. 5 N onyl 3. 5 1, 330. 5 Tertiary butyl 3. 5 1, 071. 5

Tertiary amyl 3. 5 1, 148. 5 N onyl 8. 5 1, 456. 5 Tertiary butyl 3. 5 1, 008. 5

' dehyde.

Tertiary amyl do o 3. 5 1,085. 5 N onyl 3. 5 1 393. 5 Tertiary butyl 4. 2 996. 6

Tertiary amyl 4. 2 1,083. 4 Nonyl a 4. 2 1. 430. 6 4. 8 1, 094. 4 4. 8 1, 189. 6 4. 8 1, 570. 4 1. 5 604. 1. 646. 0 1. 5 653. 0 1. 5 688. 0

2.0 692. 0 2.0 748.0 Cyclohexyl. 2. 0 740. 0

PART 5 As has been pointed out, the amine herein employed asa reactant is a basic secondary polyamine and preferably a strongly basic secondary polyamine free from hydroxyl groups, free from primary amino groups, free from substituted imid'azoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalent are alkyl alicyclic, arylalkyl, or 'heterocyclic in character.

Previous reference has been made to a number of polyamines which are satisfactory for use as reactants in the instant condensation procedure. The cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be as many as 5, 6 or 7 nitrogen atoms.

Such amines are susceptible to terminal alkylation or the equivalent, i. e., reactions which convert the ondary or tertiary amine radical. amines having at least 3 nitrogen. atoms or more, both terminal groups could be converted into tertiary groups, or one terminal group could be converted into a tertiary group and the other into a secondary amino group. By way of example the following formulas are included. It will be noted they include some polyamines which, instead of being obtained from dichloride, propylene dichloride, or the like, are obtained from dichloroethyl ethers in which the divalent radical has a carbon atom chain interrupted by an oxygen atom:

Another procedure for producing suitable polyamines is a reaction involving first an alkylene imine, such as ethylene imine or propylene imine, followed by an alkylating agent of the kind described, for example, dimethylsulfate; or else a reaction which involves an alkylene oxide, such as ethylene oxide or propylene oxide, followed by the use of an alkylating agent or the com-- parable procedure in which a halide is used.

What has been said previously may be illustrated by reactions involving a secondary alkyl amine, or a secondary aralkyl amine, or a secondary alicyclic amine. such as dibutylamine,dibenzylamine, dicyclo-hexylamine, or mixed-amines with an imine so as to introduce a primary amino group which can be reacted with an alkylating agent, such as dimethyl sulfate. In a somewhat similar procedure the secondary amine of the kind just specified can be reacted withlan alkylene oxide such as ethylene oxide, propylene oxide, or the like, and then reacted with an imine followed by the final stepnoted above in order to convert the primary amino group into a secondary amino group.

Reactions involving the same two classes of reactants previously described, i. e., ,a secondary amine plus an imine plus an alkylating agent, or a secondary amine plus an alkylene oxide plus an imine plus an alkylating agent, can be applied to another class of primary amines which are particularly desirable for the reason that they introduce a definite hydrophile effect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula:

in which 'x-is a small whole number having a'value of l or more, and may be as much as 10 or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m represents a number to 1, with the proviso that the sum of m plus m equals 2; and R has its prior significance, particularly as a hydrocarbon radical. I

The preparation of such amines has been described in the literature and particularly in two United States patents, to wit, U. 8. Nos. 2,325,514 dated July 27, 1943, to Hester, and 2,355,337, dated August8, 1944, to Spence. The latter patent describes typical haloalkyl ethers such kind above described, in which one of the groups attached to nitrogen is typified by R. Such haloalkyl ethers also can be reacted with ammonia to give secondary amines as described in the first of the two patents mentioned immediately preceding. Monoamines so obtained and suitable for conversion into appropriate polyamines are exemplified zNH.

Other somewhat similar secondary monoarnines equally suitable for such conversion reactions in order to yield appropriate secondary amines, are those of the composition 7 as described in U. S. Patent No. 2,375,659 dated May 8, 1945, to Jones et al. Inthe above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other suitable secondary amines which can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszub'a, provided there is no negative group or halogen attached to the phenolic. nucleus; Examples include the following: beta phenoxyethylamine, gamma phenoxypropylamine, beta-phenoxy-alpha-methylethylarnine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyamines are the kind described in British Patent No. 45 6,5 17 and may be illustrated by In light of the various examples of polyamines which have been used for illustration it maybe well to refer again to the fact that previously the amine was shown as amine'may yield compounds in which R and R are.

22 dissimilar This is illustrated by reference 10' two prior' examples Y 1 O H: CH1

H N propyleneN propyleneN (c mNoiHrNciHiNclnrNclmNwnm H H H In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different than if the reaction took place at the intermediatesecondary amino radical as differentiated from the terminal group. .Ag'ain, referring to the second formula above, although a t'ermi-y nal amino radical is not involved it is obvious again that one could obtain two difierent structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending whether the reaction took place at either one of the two outer secondary'aminogroups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde as illustrated by the above examples it is obvious that one might get a mixture in which in part the reaction took place at one point and in part at another point. indeed, there are well known suitable polyamine reaca tions where a large variety of compounds might be ob-: tained due to such multiplicity of reactive radicals. This can be illustrated by the following formula:

following details are included.

CH; CH!

Over and above the specific examples which have appeared previously, attention is directed to the fact that. added suitable polyamines are shown in subsequent Table IV.

PART 6 The products obtained by the hereindescribed processes represent cogeneric mixtures which are the resultof a condensation reaction or reactions. Sincethe resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difiicult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as dilferentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heat-reactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not re-- stricted to a single phase system, and since temperatures up to C. or thereabouts may be employed, it is obvious that the procedure becomes comparativelysim ple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368.- In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage ,of reaction if employed as subsequently,.described; inafact usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins'which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction'can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethylalcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively nonvolatile solvent such as dioxane or the diethylether of ethylene glycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the same sense that it is not necessary to use an initial resin which issoluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more difficult perhaps to add a solid material instead of the liquid solution, and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an ad vantage for reasons stated.

Anotherfactor, as far as the selection of solvent goes, is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solids or thick viscuous liquids in which there is some change from the initialresin itself, particularly if some of the initial solvent is apt to remain without complete removal. Even if one starts with a resin which is almost water-white in color, the products obtained are almost invariably a dark red in color or at least a red-amber, or some color which includes both an amber component and a reddish component. By and large, the melting point is apt to be lower and the products may be more sticky and more tacky than the original resin itself. Depending on the resin selected and on the amine selected the condensation product or reaction mass on a solvent-free basis may be hard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicles such as a dilute solution, for instance, a solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the tinished product into salts by simply adding a stoichi'ometric amount of any selected acid and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently-it is convenient to eliminate all solvent, using a temperature .of not over 150 C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i. e., the use of the most economical solvent and also on three other factors, two of which have been previously mentioned: (a) is the solvent to remain in the reaction mass without removal? ([2) is the reaction mass to be subjected to further reaction in which the'solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oXyalkylation); and the third factor is this, (0) is an effort to be made to purify the reaction mass by the usual procedure as, for example, a water-wash to remove the water-soluble unreacted formaldehyde, if any, or a Water-wash to remove any unreacted water-soluble polyamine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, we have found xylene the most satisfactory solvent.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the. reaction an opportunity to proceed as far as it will at some low temperature, for instance, to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. I have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde .to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then theamount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then-agi- V tation is-required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble' then agitation should be more vigorous'ffor the 7 reason that reaction probably takes place principally at p more interfacial area.

' should be long enough to insure that the resin added,

preferably in a powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solutionform, just as preparation is described in afore- After the resin is mentioned U. S. Patent 2,499,368. in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If itis not solublein 25 the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a three-phase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any difficulty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. 'The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difficulties are involved. We have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the most, up to -24 hours, we then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature we use a phaseseparating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about 100 C., and generally slightly above 100 C. and below 150 C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyarnine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the usual Ways, including the amount of 26 v water of reaction, molecular weight, and particiilarly in some instances have checked whether or not the endproduct showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if any is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1 b The phenol-aldehyde resin is the one that has been identifier. previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a preceding were powdered and mixed with a somewhat lesser weight of xylene, i. e., 600 gnams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 to 35 C. and 176 grams of symmetrical dimethylethylene diamine added. The mixture was stirred vigorously and formaldehyde added slowly. In. this particular instance the formaldehyde used was a 30% solution and 200 grams were employed which were added in a little short of 3 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 46 C. for about 19 hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn. from time to time. The presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within approximately two to three hours after refluxing started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all the water of solution zand reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately 152 C. or slightly higher. The mass was kept at this higher temperature for three to four hours and reaction stopped. During this time, any additional water which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sampie was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tack resin. The overall time for reaction was somewhat less than 30 hours. In other examples, it varied from a little over 20 hours up to 36 hours. The time can be reduced by cutting the low temperature period to approximately 3 to 6 hours.

Note that in Table IV following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water in both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of to C., or thereabouts. Usually the mixture 27 yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table IV.

valuable and. from such standpoint the herein described products may be considered as valuable intermediates. Subsequent-oxyalkylation involves the use of ethylene oxide, propylene oxide, butylene oxide, glycide, etc. Such TABLE IV Strength of Reac- Reac- Max.

Ex Resin Amt., Amine used and amount formalde- Solvent used tion, tion distill.

No used grs. hyde soln. and amt. 0. time, temp.,

and amt. hrs. 0.

882 Amine A, 176 g 30%, 200 g... Xylene, 600 g 20-23 26 152 480 Amine A, 88 g 30%, 100 g. Xylene, 450 g 20-21 24 150 633 dodo Xylene, 550 g 20-22 28 151 441 Amine B, 116 g. 37%, 81 g Xylene, 400 g 20-28 36 144 480 do ..do Xylene, 450 g 22-80 25 156 633 do "d Xylene, 600 g 21-28 32 150 882 Amine O, 204 g. 30%, 200 g ..do 21-23 30 145 480 Amine C, 102 g. 37%, 100 g. Xylene, 450 g... -25 35 148 do Xylene, 500 g 20-27 35 143 37%, 81 g Xylene, 425 g 20-22 31 145 -do Xylene, 500 gm. 21-26 24 146 Xylene, 550 g 22-25 36 151 Xylene, 400 g 25-38 32 150 do 21-24 152 Xylene, 550 g 21-26 27 145 Xylene, 400 g 20-23 25 141 do 22-27 29 143 Xylene, 450 g. 23-25 36 149 ..do 21-26 32 148 Xylene, 500 an. 21-23 30 148 do 20-26 36 152 441 do Xylene, 440 g. 21-24 32 150 Amine H, 282 g. Xylene, 500 n--- 21-28 25 150 391 do 30%, 50 g.. Xylene, 350 gm. 21-22 28 151 As to the formulas of the above amines referred to as Amine A through Amine H, inclusive, see immediately below:

oxyalkylating agents are monoepoxides as differentiated from polyepoxides.

it becomes apparent that if the product obtained is to be treated subsequently with a monoepoxide which may require a pressure vessel as in the case of ethylene oxide, it is convenient to use the same reaction vessel in both instances. modified phenol-aldehyde resin condensate would be reacted with a pclyepoxide and then subsequently with a moncepoxide. In anyevent, if desired the polycpoxide reaction can be conducted in an ordinary reaction vessel, such as thesusual glass laboratory equipment. This is particularly true-0f the kind used for resin manufacture as described in a numberof patents, as for example, U. S. Patent No; 2,499,365.

V cognizance should be taken of one particular feature in connection'with the reaction involving the polyepoxide and that is this; the amine-modified phenol-aldehyde resin condensate isinvariably basic and thus one need not add the usual catalysts which are used to promote such reactions. Generally speaking, the reaction will proceed at a satisfactory rate under suitable conditions Without any catalyst at -all.- I e Employing polyepoxides in combination-with a nonbasic reactant the usual catalysts include alkyline materials such as caustic soda, caustic potash, sodium methylate, etc. Othercatalysts may be acidic in nature and are of the kind-characterized by iron and tin chloride. Furthermore, insoluble catalysts such as clays or specially prepared mineral catalysts have been used. Iffor any reason the reaction did not proceed rapidly enough with the 'diglycidyl ether, or other analogous reactant, then a small amount of finelydivided caustic soda or sodium methyl'ate .couldbe employed as a catalyst. Theamount generally employed would be 1% or 2%.

It goes withoutsaying that'the reaction can take place in an inert solvent, i. e., one that is not oxyalkylationsusceptible. Generallyspeaking, this is most conveniently anaromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic' solventobtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar ethers, 'either'aloneor' in combination with 'a In other Words, the 2 moles of the aminehydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are to be rendered solvent-free and it is necessary that the solvent be readily removed as, for example, by the use of vacuum distillation, thus xylene or an aromatic petroleum will serve. If the product is going to be subjected to oxyalkylation subsequently, then the solvent should be one which is not oxyalkylation-susceptible. It is easy enough to select a suitable solvent if required in any instance but, everything else being equal, the solvent chosen should be the most economical one.

Example 1C The product was obtained by reaction between the diepoxide previously designated as diepoxide 3A, and condensate 2b. Condensate 2b was obtained from resin 5a. Resin 5a was obtained from tertiary eamylphenol and formaldehyde. Condensate 2b employed as reactants resin 5a and the amine designated as Amine A at the end of Table IV which is symmetrical dimethyl ethylenediamine. The amount of resin employed was 882 grams; the amount of symmetrical dimethyl ethylenediamine employed was 176' grams; and the amount of 30% formaldehyde employed was 200 grams. The amount of solvent was approximately 600 grams. All this has been described previously.

The solution of the condensate in xylene was adjusted about 118 C. The 'was"allowed to reflux at a temperature of about 128 C. using a phase-separating rose to a maximum of 160 C. The mixture was then refluxed at 160 C. for about 6 hours until the reaction stopped and the xylene which had, been removed during.

the reflux period was returned to the mixture. A small amount of material was withdrawn and the xylene evaporated on the hot plate in order to examine the physical properties. The material was a dark red viscous semisolid. It was insoluble in water, it was insoluble in 5% gluconic acid, and it was soluble in xylene, and particularly in a mixture of xylene and 20% methanol.

However, if the material was dissolved in an oxygenated solvent and then shaken with 5% gluconic acid it showed a definite tendency to disperse, suspend, or form a sol, and particularly in a xylene-methanol mixed solvent as previously described, with or without the further addition of a little acetone.

The procedure employed of course is simple in light of What has been said previously and in effect is a procedure similar to that employed in the use of glycide or methyl-glycide as oxyalkylating agents. See, for example, Part 1 of U. S. Patent No. 2,602,062, dated July 1, 1952, to De Groote.

Various examples obtained in substantially the same manner are enumerated in the following tables:

TABLE V Con- Diep- Time Max. Ex. den- Amt., oxide Amt, Xylene, Molar of reactemp., Color and physical state No. sate grs. used grs. 'grs. ratio tion, 0.

used hrs.

116 8A 17 133 2:1 6 160 Dark semi-solid. 122 3A 17 139 2:1 7 165 D0. 111 3A 17 128 2:1 6 162 Do. 119 3A 17 136 2: 1 6 170 Do. 3A 17 137 2:1 6 160 D0. 159 3A 17 176 2:1 8 168 Dark solid mass. 122 3A 17 139 2:1 7 165 D0. 143 3A 17 160 2:1 8 170 Do. 3A 17 157 2:1 8 162 D0. 146 3A 17 163 2: 1 8 165 Do.

TABLE VI Con- Diep- Time Max. Ex. den- Amt, oxide Amt. Xylene, Molar of reactemp., Color and physical state No. sate grs. used grs. grs. ratio tion, 0.

used hrs.

1D 116 B1 27. 5 143. 5 2:1 7 162 Dark semi-solid. 2D 122 B1 27. 5 149.5 2:1 6 166 Do. 3D 111 B1 27. 5 138. 5 2: 1 7 D0. 4D 119 B1 27. 5 146. 5 2: 1 8 Do. 5D 120 B1 27.5 147. 5 2: 1 8 168 Do. 6D 169 B1 27. 5 186. 5 2:1 8 160 Dark solid mass. 7D 122 B1 27. 5 149. 5 2: 1 7 160 D0. SD 143 B1 27. 5 170. 5 2:1 8 162 Do. 9D 140 B1 27. 5 167. 5 2:1 8 160 Do. 10D--- 20b 146 B1 27. 5 173. 5 2:1 8 165 Do.

to a 50% solution. In this particular instance, and in practically all the others which appear in a subsequent 60 table, the examples are characterized by the fact that no alkaline catalyst was added. The reason is, of course, that the condensate as such is strongly basic. If desired, a small amount of an alkaline catalyst could be added, such as finely powdered caustic soda, sodium methylate, etc. If such alkaline catalyst is added it may speed up the reaction but it also may cause an undesirable reaction, such as the polymerization .of a diepoxide.

In any event, 116 grams of the condensate dissolved in approximately 116 grams of xylene were stirred and heated to 100 C. 17 grams of the diepoxide previously identified as 3A and dissolved in an equal weight of xylene were added dropwise. An initial addition of the xylene solution carried the temperature to 109 C. The remainder of diepoxide was added in approximately one hours time. During this period the temperature rose to Solubility in regard to all these compounds was substantially similar to that which was described in Example C.

TABLE VII Probable Probable Resin conmol. wt. of Amt. of Amt. of number of 65 Ex. No. densate reaction product, solvent, hydroxyls used product grs. grs. I per-moleeule 2, 660 2, 665 1, 335 11 2, 772 2, 780 1, 394 11 2, 560 2, 564 1,284 11 2, 716 2, 720 1, 362 11 2, 748 2, 750 1, 376 11 3, 516 3, 522 1, 762 ll 2, 784 2,790 1,398 i 11 3,196 3,200 '1, 602 11. 3,144 150 1, 578 12 v 3, 252 3, 250 1, 624 12 TABLE VIII Probable Probable Resin conmol. wt. of Amt. of Amt. of number of Ex. No densate reaction product, solvent, hydroxyls used product grs. grs. per molecule At this point it may be desirable to direct attention to two facts, the first being that we are aware that other diepoxides free from an aromatic radical as, for example, epoxides derived from ethylene glycol, glycerine, or the like, such as the following;

may be employed to replace the diepoxides herein described. However, such derivatives are not included as part of the instant invention. 7

At times we have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the diethyl ether of ethylene glycol may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reaction by adding a small amount of initially lower boiling solvent such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than apparently the theoretical amount of diepoxide, for instance, 90% to 95% instead of 100%. The reason for this fact may reside in the possibility that the molecular weight dimensions on either.

the resin molecule or the diepoxide molecule may actually vary from the true molecular weight by several percent.

Previously the condensate has been depicted in a simplified form which, for convenience, may be shown thus:

(A1nine)CH (Resin)CH (Amine) Following such simplification the reaction product with a polyepoxide and particularly a diepoxide, would be indicated thus:

[(Amine) CHAResin) CH (Amine) in which D. G. E. represents a diglycidyl ether as specified. If the amine happened to have more than one reactive hydrogen, as in the case of a hydroxylated amine 01' poly- [(Amine) 0H (Resin) CH1 (Amine) 'amine, having a multiplicity of secondary amino groups it A CH (Amine)] mine) 1 [(Amine) CHdAmine) 1 [(Resin) CH;;(Resin)] I: (Amine) GH (Amine)] g n G. a

I: (Resin) CHAResin) PART 8 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known thatconventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent inso-lubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials of our invention when employed as demulsifying agents.

The materials of our invention, when employed as treating or demulsifying agents, are used in the conventional way, well known to the art, described, for example, in

Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application'of heat, and allowing the mixture to stratify. a I

As noted above, the products herein described may be used not onlyin diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

The product of the present invention, for example, the product of Example 1c, 20%;

A cyclohexylamine salt of a polypropylated napthalene monosulfonic acid, 2 4%;

An ammonium salt of a monosulfonicacid,:24%;

A sodium salt of oil-soluble mahogany petroleum sulfonicacid, 12%; V V

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol,,5%.

The above proportions are all-weight percents.

polypropylated napthalene PART 9 The products herein described as such and prepared in accordance with. this invention can be used as emulsifying agents,.for oils, fats and waxes, as ingredients in insecticide compositions, or as detergents and wetting agents in the laundering, scouring, dyeing, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Other uses include the preparation or resolution of petroleum emulsions, whether of the water-in-oil type or oil-in-Water type. They may beused as additives in connection with other emulsifying agents; they may be employed to contribute hydrotropic effects; they may be used as anti-strippers in connection with asphalts; they may be used to prevent corrosion, particularly the corrosion of ferrous metals for various purposes and particularly in connection with the production of oil and gas;

fluids of the aqueous or nonaqueous type, some have definite anti-corrosive action. They may be used also in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasingthe ultimate fiow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters. They can also be used in dry cleaners soaps.

With regard to the above statements, reference is made particularly to the use of the materials as such, or in V the form of a salt; the salt form refers to a salt involving either one. or both basic nitrogen atoms. Obviously, the salt form involves a modification in which the hydrophile character can be either increased or decreased and, inversely, the hydrophobe character can-be decreasedor increased. .For example, neutralizing the product with practically-any low molal acid, such asacetic acid, hydroxyacetic acid, lactic acid, or nitric'acid, is apt to markedly increase the hydrophile effect. One may also use acids of the type a a-o-cn -crr omn -cn -o-crr co0H in which R is a comparatively small alkyl radical, such as methyl, ethyl or propyl. The hydrophile effect may be decreased and the hydrophobe effect increased by neutralization with a monocarboxy detergent-forming acid. These are acids whichhave at least 8 and not more than 32 carbon atoms. They are obtained from higher fatty acids andinclude also resin'acids such as abietic acid, and petroleum acids such as naphthenic acids and acids obtained by the oxidation of wax. One can also obtain new products having unique properties by combination with polybasic acids, such as digly colic acid, oxalic acid, dimerized acids from linseed oil; etc. The most common examples, of course, are the higher fatty acids having generallylO to.18' carbon atoms. We have found that a particularly-valuable anti-corrosive agent can be obtained from any suitable resin and formaldehyde provided the secondary amine is dicyclohexylamine. The corrosion-inhibiting properties of this'compound can be increased by neutralization with either one orftwo moles of, an oil-soluble sulfonicacid, particularly a sulfonic acid ofthe type known as mahogany sulfonic acid. j

The oil-soluble sulfonic acidspreviously referred, to maybe synthetically derived by sulfonating olefins, aliphatic, fatty acids, or their esters, alkylated aromatics or their hydroxyl derivatives,'partially hydrogenated aromatics, etc., with sulfuric acid or other sulfonating agents.

(R) nOSOaH where (R),, is one or more alkyl, alkaryl or aralkyl groups and the aromatic nucleus may be a single or condensed ring or a partially hydrogenated ring. The lower molecular weight acids can be extracted from the acid treated oil by adding a small amount of water, preferably after dilution of the oil withkerosene. However, the more desirable high molecular weight (350-500) acids, particularly those produced when treating petroleum distillates with fuming acid to produce white oil, are normally'recovered as sodium soaps by neutralizing the acid oil with sodium hydroxide or carbonate and extracting with aqueous alcohol. The crude soap extract is first recovered as a water cured after removal of alcohol by distillation and a gravity separation of some of the contaminating salts (sodium carbonate, sulfates and sulfites). These materials still contain considerable i quantitiesof salts and consequently are normally purified by additionof a more concentrated alcohol followed by storage to permit settling of salt brine. The alcohol and water are then stripped out and the sodium salts so obtained converted into free acids.

Not only can one obtain by-product sulfonic acids of the mahogany type which are perfectly satisfactory and within the molecular range of 300 to 600 but also one enhanced in comparison with the resin as such. Av

procedure designed primarily to enhance the hydrophobe properties of the resin involves derivatives obtained by a phenyl or substituted phenyl glycidyl ether of the structure in which R represents a hydrocarbon substituent such as an alkyl radical having 1 to 24 carbon atoms, or a cyclic group, such as a cyclohexyl group, a phenyl group, or a benzyl group, and n represents 0, 1, 2 or 3. n is zero in the instance of the unsubstituted phenyl radical. Such compounds are in essence oxyalkylating agents and reaction involves the introduction of a hydrophobe group and the formation of an alkanol hydroxyl radical.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the Water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., combination of water or particularly in the form of a low molal organic acid such as the acetate or hydroxy-acetate, have sufficiently hydrophile character to at least meet the test set forth inU. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patentsuch test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface acivity.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

l. The method of (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble,- low-stage phenol-aldehyde resin 35 having an average *molecular'weig ht corresponding to at least '3 and not over '6 phenolic nuclei per resin molecule; said resin being difunctional only in regardto'methylolforming reactivity; said resin being derived by reaction between 21 difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms-and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free'from any primary amino radical, any substituted imidazolineradical, and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be beatstable and oxyalkylation-susceptible; followed by (B) reacting said resin condensate with a phenolic polyepoxide containing at least two 1,2-epoxy rings and being free from reactive functional groups other than 1,2- epoxy and hydroxyl groups and cogenerically associated compounds formed in the preparation of said polyepoxides; said epoxides being monomers and low molal polymers not exceeding the tetramers; said polyepoxides being selected from the class consisting of (aa) compounds where thephenolic nuclei are directly joined without an intervening bridge radical, and (b5) compounds containing a radical in which 2 phenolic nuclei are 'joined by a divalent radical selected from the class consisting of ketone residues formed by the eliminationtof the ketonic oxygen atom, and aldehyde residues, obtained by the elimination of the aldehyde oxygen atom, the

divalent-radical i the divalent radical, the divalent sulfone'radical, and the divalent monosulfide radical S-, the divalent radical -CH SCH and the divalent disulfide radical -S-:S; said phenolic portion of the diepoxide being obtained from a phenol of the structure i III in which R, R, and R represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermos'etting organic solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be approximately 2 moles of the resin condensate' per mole of-the phenolic polyepoxide.

in which R is an aliphatic hydrocarbon, radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not'over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical;

and (0') formaldehyde; said condensationreaction being conducted at a temperature sulhciently high to eliminate water and below the pyrolytic point of the reactants and resultants (of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting a phenolic diepoxide containing two 1,2-epoxy rings and being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups, and cogenerically associated compounds formed in the preparation of said diepoxides; said epoxides being selected trom the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (bb) compounds containing a radical in which 2 phenolicfnuclei are joined by ajdivalent radical selected from the class consisting of ketone residues J-formedby theclimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehydicoxygenatom, the divalent radical thedivalent V i a radical, the divalentsulfone radicaLVand the divalent monosulfide radical S-, the divalent radical CH SCH i and .the divalentdisulfide radical -SS-; said phenolic portion ,of the diepoxide being obtained .from a phenol of the structure in which R, R", and R' represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said'substituent member having not --over 18 carbon atoms; the molar ratio of reactant (A) to reactant (B) being approximately 2 to 1 respectively; with the further proviso that said reactive compound (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product. 'be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

3. The method of (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the sub stantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32' carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting a member of the class consisting of (aa) compounds of the following formula in which R, represents a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical the divalent radical, the divalent sulfone radical, and the divalent monosulfide radical S, the divalent radical CH SCH and the divalent disulfide radical -SS; and R 0 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol in which R, R", and R represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; n represents an integer selected from the class of zero and 1, and n represents a whole number not greater than 3; and (bb) cogenerically associated compounds formed in the preparation mately 2 to 1 respectively; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solventsoluble liquids and low-melting solids; With the final proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and resultants of reaction.

4. The method of (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyderesin having an average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by (B) reacting a member of the class consisting of (aa) compounds of the following formula wherein R is an aliphatic hydrocarbon bridge, each n independently has one of the values 0 to 1, and R is an alkyl radical containing from 1 to 12 carbon atoms, and (bb) cogenerically associated compounds formed in the preparation of (aa) preceding, including monoepoxides; with the proviso that (B) consist principally of the monomer as distinguished from other cogeners; the molar ratio of reactant (A) to reactant (B) being approximately 2 to 1 respectively, with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

5. The method of (A) condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, Water-insoluble, low-stage phenol-aldehyde resin having an average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting a member of the class consisting of (an) compounds of the following formula and (bb) cogenerically associated compounds formed in the preparation of (aa) preceding, including monoepoxides; with the proviso that (B) consist principally of the monomer as distinguished from other cogeners; the molar 3 ratio of reactant (A) to reactant (B) being approximately 2 to 1 respectively with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that in the substituent radical and the precursory aldehyderis formaldehyde.

8. The product obtained by the method described in claim 1.

9. The product obtained by the method described in claim 2.

10. The product obtained by the method described in claim 3. 5

11. The product obtained by the method described in claim 4. V

12. The product obtained by the method described in claim 5.

13. The product obtained by the method described in claim 6.

14. The product obtained by the method described in claim 7. 7

Greenlee Sept. 12, 1950 De Groote Apr. 24, 1956 

1. THE METHOD OF (A) CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENTSOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOLFORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 